Partially dehydrated reaction product, process for making same, and emulsion containing same

ABSTRACT

The disclosed invention relates to a composition comprising a partially dehydrated product made by:  
     (I) reacting (A) a hydrocarbyl substituted succinic acid or anhydride with (B) a polyol, a polyamine, a hydroxyamine, or a mixture of two or more thereof, to form a first intermediate product comprising: an ester, partial ester or mixture thereof when (B) is a polyol; an amide, imide, salt, amide/salt, partial amide or mixture of two or more thereof when (B) is a polyamine; or an ester, partial ester, amide, partial amide, amide/salt, imide, ester/salt, salt or a mixture of two or more thereof when (B) is a hydroxyamine, a mixture of a polyol and a polyamine, a mixture of a polyol and a hydroxyamine, a mixture of a polyamine and a hydroxyamine, or a mixture of a polyol, a polyamine and a hydroxyamine; the hydrocarbyl substituent of said acid or anhydride having an average of about 8 to about 200 carbon atoms; and  
     (II) heating said first intermediate product at an effective temperature to form a second intermediate product with water of reaction being formed, and separating a portion of said water of reaction from said second intermediate product, when (A) is said succinic anhydride the amount of water of reaction that is separated is from about 0.2 to about 0.9 equivalents of said water of reaction per equivalent of said succinic anhydride, when (A) is said succinic acid the amount of water of reaction that is separated is from about 1.2 to about 1.9 moles of said water of reaction per equivalent of said succinic acid, said partially dehydrated product having a total acid number in the range of about 20 to about 100 mg of KOH/g.  
     A process for making the foregoing partially dehydrated product is also disclosed. Emulsions comprising an organic phase, an aqueous phase, and an emulsifying amount of the foregoing partially dehydrated product are disclosed.

TECHNICAL FIELD

[0001] This invention relates to partially dehydrated reaction productsderived from (A) a hydrocarbyl substituted succinic acid or anhydride,and (B) a polyol, polyamine, hydroxyamine or mixture of two or morethereof. The invention also relates to a process for making thesepartially dehydrated reaction products. The inventive reaction productsare useful as emulsifiers in making emulsions, especially explosiveemulsions and emulsion fertilizers.

BACKGROUND OF THE INVENTION

[0002] Explosive emulsions typically comprise a continuous organic phaseand a discontinuous oxidizer phase containing water and anoxygen-supplying source such as ammonium nitrate, and an emulsifier.Examples of such explosive emulsions are disclosed, inter alia, in U.S.Pat. Nos. 4,708,753 and 5,920,031. In U.S. Pat. No. 4,708,753 theemulsifier is a salt derived from a hydrocarbyl-substituted carboxylicacid or anhydride, or ester or amide derivative of said acid oranhydride, the hydrocarbyl substituent having an average of from about20 to about 500 carbon atoms, and an amine. In U.S. Pat. No. 5,920,031the emulsifier is the product made by the reaction of component (A) withcomponent (B). Component (A) is a substituted succinic acylating agent,said substituted succinic acylating agent consisting of substituentgroups and succinic groups wherein the substituent groups are derivedfrom a polyalkene, said acylating agents being characterized by thepresence within their structure of an average of at least 1.3 succinicgroups for each equivalent weight of substituent groups. Component (B)is ammonia and/or a mono-amine.

[0003] U.S. Pat. No. 5,512,079 discloses an emulsion fertilizercomprising a discontinuous aqueous phase comprising at least onefertilizer component such as ammonium nitrate; a continuous oil phase;and an emulsifier. The emulsifier is the reaction product of ahydrocarbyl substituted succinic anhydride acylating agent and atertiary alkanol amine.

[0004] A problem in the explosive emulsion and emulsion fertilizer artsrelates to the fact that it is desirable to lower the viscosities of theemulsions in order to improve their pumping and handlingcharacteristics. It is also desirable to make emulsions with relativelyhigh aqueous phase to organic phase weight ratios. This is advantageouswith explosive emulsions because it permits the delivery of more of theoxygen-supplying source with the same weight of emulsion. Similarly,this is advantageous with emulsion fertilizers because it permits thedelivery of more of the fertilizer component with the same weight ofemulsion. Unexpectedly, by use of the inventive reaction products asemulsifiers it is possible to formulate explosive emulsions and emulsionfertilizers having these characteristics. Going beyond explosiveemulsions and emulsion fertilizers, the inventive reaction products areuseful as emulsifiers in a wide variety of applications.

[0005] PCT publication WO96/25384 discloses monomeric, oligomeric andpolymeric bisesters of alkyl- or alkenyldicarboxylic acid derivativesand polyalcohols, and their use as solubilizers, emulsifiers and/ordetergents. The bisesters are described as being useful in formulatingcosmetic compositions, detergents and cleaners, pharmaceuticalcompositions, foodstuffs and crop protection compositions. A process forpreparing these bisesters is disclosed.

SUMMARY OF THE INVENTION

[0006] This invention relates to a composition comprising a partiallydehydrated product made by:

[0007] (I) reacting (A) a hydrocarbyl substituted succinic acid oranhydride with (B) a polyol, a polyamine, a hydroxyamine, or a mixtureof two or more thereof, to form a first intermediate product comprising:an ester, partial ester or mixture thereof when (B) is a polyol; anamide, imide, salt, amide/salt, partial amide or mixture of two or morethereof when (B) is a polyamine; or an ester, partial ester, amide,partial amide, amide/salt, imide, ester/salt, salt or a mixture of twoor more thereof when (B) is a hydroxyamine, a mixture of a polyol and apolyamine, a mixture of a polyol and a hydroxyamine, a mixture of apolyamine and a hydroxyamine, or a mixture of a polyol, a polyamine anda hydroxyamine; the hydrocarbyl substitutent of said acid or anhydridehaving an average of about 8 to about 200 carbon atoms; and

[0008] (II) heating said first intermediate product at an effectivetemperature to form a second intermediate product with water of reactionbeing formed, and separating a portion of said water of reaction fromsaid second intermediate product to form said partially dehydratedproduct, when (A) is said succinic anhydride the amount of water ofreaction that is separated is from about 0.2 to about 0.9 moles of saidwater of reaction per equivalent of said succinic anhydride, when (A) issaid succinic acid the amount of water of reaction that is separated isfrom about 1.2 to about 1.9 moles of said water of reaction perequivalent of said succinic acid, said partially dehydrated producthaving an acid number in the range of about 20 to about 100 mg of KOH/g.

[0009] This invention also relates to a process, comprising:

[0010] (I) reacting (A) a hydrocarbyl substituted succinic acid oranhydride with (B) a polyol, a polyamine, a hydroxyamine, or a mixtureof two or more thereof, to form a first intermediate product comprising:an ester, partial ester or mixture thereof when (B) is a polyol; anamide, imide, salt, amide/salt, partial amide or mixture of two or morethereof when (B) is a polyamine; or an ester, partial ester, amide,partial amide, amide/salt, imide, ester/salt, salt or a mixture of twoor more thereof when (B) is a hydroxyamine; a mixture of a polyol and apolyamine, a mixture of a polyol and a hydroxyamine, a mixture of apolyamine and a hydroxyamine, or a mixture of a polyol, a polyamine anda hydroxyamine; the hydrocarbyl substituent of said acid or anhydridehaving an average of about 8 to about 200 carbon atoms; and

[0011] (II) heating said first intermediate product at an effectivetemperature to form a second intermediate product with water of reactionbeing formed, and separating a portion of said water of reaction fromsaid second intermediate product to form said partially dehydratedproduct, when (A) is said succinic anhydride the amount of water ofreaction that is separated is from about 0.2 to about 0.9 equivalents ofsaid water of reaction per equivalent of said succinic anhydride, when(A) is said succinic acid the amount of water of reaction that isseparated is from about 1.2 to about 1.9 moles of said water of reactionper equivalent of said succinic acid, said partially dehydrated producthaving a total acid number in the range of about 20 to about 100 mg ofKOH/g.

[0012] This invention also relates to emulsions, comprising: an organicphase; an aqueous phase; and an emulsifying amount of the foregoingpartially dehydrated product.

[0013] As indicated above, the inventive partially dehydrated reactionproducts are useful as emulsifiers in formulating emulsions for a widevariety of applications. These include one or more of the following:lubricants or functional fluids; fuels; paints; coatings; inks; caulksor adhesives; fertilizers or agricultural chemicals; refinery oroil-field products; mining products; explosives; commodity chemicalmanufacturing processes; processes involving the use of emulsionscontaining 2-acrylamido-2-methyl-1-propane sulfonic acid monomer; andthe like.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] As used herein, the terms hydrocarbyl substituent, hydrocarbylgroup, hydrocarbon group, and the like, are used to refer to a grouphaving one or more carbon atoms directly attached to the remainder of amolecule and having a hydrocarbon or predominantly hydrocarboncharacter. Examples include:

[0015] (1) purely hydrocarbon groups, that is, aliphatic (e.g., alkyl,alkenyl or alkylene), alicyclic (e.g., cycloalkyl, cycloalkenyl) groups,aromatic groups, and aromatic-, aliphatic-, and alicyclic-substitutedaromatic groups, as well as cyclic groups wherein the ring is completedthrough another portion of the molecule (e.g., two substituents togetherforming an alicyclic group);

[0016] (2) substituted hydrocarbon groups, that is, hydrocarbon groupscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thegroup (e.g., halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro,nitroso, and sulfoxy);

[0017] (3) hetero substituted hydrocarbon groups, that is, hydrocarbongroups containing substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen. In general, no more thantwo, and in one embodiment no more than one, non-hydrocarbon substituentis present for every ten carbon atoms in the hydrocarbon group.

[0018] The term “lower” when used in conjunction with terms such asalkyl, alkenyl, alkoxy, and the like, is intended to describe suchgroups that contain a total of up to 7 carbon atoms.

[0019] The term “water-soluble” refers to materials that are soluble inwater to the extent of at least one gram per 100 milliliters of water at25° C.

[0020] The term “oil soluble” refers to materials that are soluble inmineral oil to the extent of at least one gram per 100 milliliters ofmineral oil at 25° C.

[0021] The term “total acid number” (TAN) refers to a measure of theamount of potassium hydroxide (KOH) needed to neutralize all of theacidity of a product or a composition. The sample to be tested isdissolved in a toluene and tert-butyl alcohol solvent and titratedpotentiometrically with a solution of tetra-n-butylammonium hydroxide.The toluene and tert-butyl alcohol solvent is prepared by diluting 100ml of 25% methanolic tert-butyl alcohol and 200 ml of isopropyl alcoholto one liter total volume with toluene. The solution oftetra-n-butylammonium hydroxide is a 25% by weight solution in methylalcohol. A Metrohm Standard pH Combination Glass Electrode EA 120 (3Maq. KCl), which is a combination glass-plus-reference electrode, isused. The end-points corresponding to the inflections are obtained fromthe titration curve and the acid numbers calculated.

[0022] The term “total base number” (TBN) refers to a measure of theamount of acid (perchloric or hydorchloric) needed to neutralize thebasicity of a product or a composition, expressed as KOH equivalents. Itis measured using Test Method ASTM D 2896.

[0023] The number of “equivalents” of a hydrocarbyl substituted succinicacid or anhydride is dependent on the number of carboxylic functions(e.g., —C(═O)—) present in the acid or anhydride. Thus, the number ofequivalents of acid or anhydride will vary with the number of succinicgroups present therein. In determining the number of equivalents of acidor anhydride, those carboxylic functions which are not capable ofreacting with the polyol, polyamine or hydroxyamine (B) are excluded. Ingeneral, however, there are two equivalents of acid or anhydride foreach succinic group in the acid or anhydride. Conventional techniquesare readily available for determining the number of carboxylic functions(e.g., acid number, saponification number) and, thus, the number ofequivalents of the acid or anhydride available to react with component(B).

[0024] An “equivalent” of a polyol is that amount of polyolcorresponding to the total weight of polyol divided by the total numberof hydroxyl groups present. Thus, glycerol has an equivalent weightequal to one-third its molecular weight.

[0025] An “equivalent” of a polyamine is that amount of polyaminecorresponding to the total weight of the polyamine divided by the numberof nitrogen atoms present which are capable of reacting with ahydrocarbyl substituted succinic acid or anhydride. Thus, octylamine hasan equivalent weight equal to its molecular weight; ethylene diamine hasan equivalent weight equal to one-half of its molecular weight. Theequivalent weight of a commercially available mixture of polyalkylenepolyamines can be determined by dividing the atomic weight of nitrogen(14) by the % N contained in the polyamine; thus, a polyalkylenepolyamine mixture having a % N of 34 would have an equivalent weight of41.2.

[0026] An “equivalent” of a hydroxyamine is that amount of hydroxyaminecorresponding to the total weight of hydroxyamine divided by the numberof hydroxyl groups and nitrogen atoms present which are capable ofreacting with a hydrocarbyl substituted succinic acid or anhydride.Thus, diethanolamine has an equivalent weight equal to one-third itsmolecular weight.

[0027] The Partially Dehydrated Reaction Product

[0028] The hydrocarbyl substituted succinic acid or anhydride (A) may berepresented by the formulae

[0029] wherein in each of the above formulae, R is a hydrocarbyl groupof about 12 to about 200 carbon atoms, and in one embodiment about 12 toabout 150 carbon atoms, and in one embodiment about 12 to about 100carbon atoms, and in one embodiment about 12 to about 75 carbon atoms,and in one embodiment about 12 to about 50 carbon atoms, and in oneembodiment about 18 to about 30 carbon atoms. In one embodiment, R is analkyl or an alkenyl group.

[0030] In one embodiment, a mixture of at least two hydrocarbylsubstituted succinic acids or anhydrides is used. The hydrocarbylsubstituent of one of the acids or anhydrides has an average of about 12to about 24 carbon atoms, and in one embodiment about 14 to about 18carbon atoms, and in one embodiment at 16 carbon atoms. The hydrocarbylsubstituent of the other acid or anhydride has an average of about 60 toabout 200 carbon atoms, and in one embodiment about 60 to about 150carbon atoms, and in one embodiment about 60 to about 100 carbon atoms,and in one embodiment about 60 to about 75 carbon atoms.

[0031] The hydrocarbyl group R in the above formulae may be derived froman alpha-olefin or an alpha-olefin fraction. The alpha-olefins include1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-triacontene, andthe like. The alpha olefin fractions that are useful include C₁₅₋₁₈alpha-olefins, C₁₂₋₁₆ alpha-olefins, C₁₄₋₁₆ alpha-olefins, C₁₄₋₁₈alpha-olefins, C₁₆₋₁₈ alpha-olefins, C₁₈₋₂₄ alpha-olefins, C₁₈₋₃₀alpha-olefins, and the like. Mixtures of two or more of any of theforegoing alpha-olefins or alpha-olefin fractions may be used.

[0032] In one embodiment, R in the above formulae is a hydrocarbyl groupderived from an olefin oligomer or polymer. The olefin oligomer orpolymer may be derived from an olefin monomer of 2 to about 10 carbonatoms, and in one embodiment about 3 to about 6 carbon atoms, and in oneembodiment about 4 carbon atoms. Examples of the monomers includeethylene; propylene; butene-1; butene-2; isobutene; pentene-1;heptene-1; octene-1; nonene-1; decene-1; pentene-2; or a mixture of twoof more thereof.

[0033] In one embodiment, R in the above formulae is a polyisobutenegroup. The polyisobutene group may be made by the polymerization of a C₄refinery stream having a butene content of about 35 to about 75% byweight and an isobutene content of about 30 to about 60% by weight.

[0034] In one embodiment, R in the above formulae is a polyisobutenegroup derived from a polyisobutene having a high methylvinylidene isomercontent, that is, at least about 50% and in one embodiment at leastabout 70% methylvinylidenes. Suitable high methylvinylidenepolyisobutenes include those prepared using boron trifluoride catalysts.The preparation of such polyisobutenes in which the methylvinylideneisomer comprises a high percentage of the total olefin composition isdescribed in U.S. Pat. Nos. 4,152,499 and 4,605,808, the disclosure ofeach of which are incorporated herein by reference.

[0035] In one embodiment, the hydrocarbyl-substituted succinic acid oranhydride (A) consists of hydrocarbyl substituent groups and succinicgroups. The hydrocarbyl substituent groups are derived from an olefinpolymer as discussed above and, in one embodiment, have a number averagemolecular weight in the range of about 750 to about 3000, and in oneembodiment about 900 to about 2000. The hydrocarbyl substituted succinicacid or anhydride is characterized by the presence within its structureof an average of at least about 1.3 succinic groups, and in oneembodiment from about 1.5 to about 2.5, and in one embodiment form about1.7 to about 2.1 succinic groups for each equivalent weight of thehydrocarbyl substituent.

[0036] For purposes of this invention, the equivalent weight of thehydrocarbyl substituent group of the hydrocarbyl-substituted succinicacid or anhydride is deemed to be the number obtained by dividing thenumber average molecular weight (M_(n)) of the polyolefin from which thehydrocarbyl substituent is derived into the total weight of all thehydrocarbyl substituent groups present in the hydrocarbyl-substitutedsuccinic acid or anhydride. Thus, if a hydrocarbyl-substituted acylatingagent is characterized by a total weight of all hydrocarbyl substituentsof 40,000 and the M_(n) value for the polyolefin from which thehydrocarbyl substituent groups are derived is 2000, then thatsubstituted succinic acid or anhydride is characterized by a total of 20(40,000/2000=20) equivalent weights of substituent groups.

[0037] The ratio of succinic groups to equivalent of substituent groupspresent in the hydrocarbyl-substituted succinic acid or anhydride (alsocalled the “succination ratio”) may be determined by one skilled in theart using conventional techniques (such as from saponification or acidnumbers). For example, the formula below can be used to calculate thesuccination ratio where maleic anhydride is used.${SR} = \frac{M_{n} \times \left( {{{Sap}.\quad {No}.\quad {of}}\quad {acylating}\quad {agent}} \right)}{\left( {56100 \times 2} \right) - \left( {98 \times {{Sap}.\quad {No}.\quad {of}}\quad {acylating}\quad {agent}} \right)}$

[0038] In this equation, SR is the succination ratio, M_(n) is thenumber average molecular weight, and Sap. No. is the saponificationnumber. In the above equation, Sap. No. of acylating agent=measured Sap.No. of the final reaction mixture/Al wherein Al is the active ingredientcontent expressed as a number between 0 and 1, but not equal to zero.Thus an active ingredient content of 80% corresponds to an Al value of0.8. The Al value can be calculated by using techniques such as columnchromatography which can be used to determine the amount of unreactedpolyalkene in the final reaction mixture. As a rough approximation, thevalue of Al is determined after subtracting the percentage of unreactedpolyalkene from 100.

[0039] In one embodiment, the polyol (B) is a compound represented bythe formula

R—(OH)_(m)

[0040] wherein in the foregoing formula, R is an organic group having avalency of m, R is joined to the OH groups through carbon-to-oxygenbonds, and m is an integer from 2 to about 10, and in one embodiment 2to about 6. The polyol may be a glycol, a polyoxyalkylene glycol, acarbohydrate, or a partially esterfied polyhydric alcohol. Examples ofthe polyols that may be used include ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol, tripropylene glycol, dibutylene glycol, tributylene glycol,1,2-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-hexanediol,1,2-cyclohexanediol, pentaerythritol, dipentaerythritol,1,7-heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol,1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol,1,2,4-butanetriol, 2,2,6,6-tetrakis-(hydroxymethyl) cyclohexanol,1,10-decanediol, digitalose,2-hydroxymethyl-2-methyl-1,3-propanediol-(tri-methylolethane), or2-hydroxymethyl-2-ethyl-1,3-propanediol-(tri-methylopropane), and thelike. Mixtures of two or more of the foregoing can be used.

[0041] In one embodiment, the polyol is a sugar, starch or mixturethereof. Examples of these include erythritol, threitol, adonitol,arabitol, xylitol, sorbitol, mannitol, erythrose, fucose, ribose,xylulose, arabinose, xylose, glycose, fructose, sorbose, mannose,sorbitan, glucosamine, sucrose, rhamnose, glyceraldehyde, galactose, andthe like. Mixtures of two or more of the foregoing can be used.

[0042] In one embodiment, the polyol is a compound represented by theformula

HO(CH₂CH(OH)CH₂O)_(n)H

[0043] wherein n is a number in the range of 1 to about 5, and in oneembodiment 1 to about 3. Examples include glycerol, diglycerol,triglycerol, and the like. Mixtures as well as isomers of the foregoingmay be used.

[0044] In one embodiment, the polyol is a polyhydric alcohol having atleast three hydroxyl groups, wherein some of the hydroxyl groups areesterfied with an aliphatic monocarboxylic acid of about 8 to about 30carbon atoms, but at least two of the hydroxyl groups are not esterfied.Examples include monooleate of glycerol, monostearate of glycerol,monooleate of sorbitol, distearate of sorbitol, di-dodecanoate oferythritol, the like. Mixtures of two or more of the foregoing can beused.

[0045] The polyamine (B) may be aliphatic, cycloaliphatic, heterocyclicor aromatic compound. Examples include alkylene polyamines andheterocyclic polyamines. The alkylene polyamines may be represented bythe formula

[0046] wherein n has an average value between 1 and about 10, and in oneembodiment about 2 to about 7, the “Alkylene” group has from 1 to about10 carbon atoms, and in one embodiment about 2 to about 6 carbon atoms,and each R is independently hydrogen or an aliphatic orhydroxy-substituted aliphatic group of up to about 30 carbon atoms.These alkylene polyamines include ethylene polyamines, butylenepolyamines, propylene polyamines, pentylene polyamines, etc. The higherhomologs and related heterocyclic amines such as piperazines and N-aminoalkyl-substituted piperazines are also included. Specific examples ofsuch polyamines include ethylene diamine, triethylene tetramine,tris-(2-amino ethyl)amine, propylene diamine, trimethylene diamine,tripropylene tetramine, tetraethylene pentamine, hexa-ethyleneheptamine, pentaethylene hexamine, or a mixture of two or more thereof.

[0047] Ethylene polyamines, such as some of those mentioned above, areuseful. Such polyamines are described in detail under the headingEthylene Amines in Kirk Othmer's “Encyclopedia of Chemical Technology”,2nd Edition, Vol. 7, pages 22-37, Interscience Publishers, New York(1965). Such polyamines are most conveniently prepared by the reactionof ethylene dichloride with ammonia or by reaction of an ethylene iminewith a ring opening reagent such as water, ammonia, etc. These reactionsresult in the production of a complex mixture of polyalkylene polyaminesincluding cyclic condensation products such as piperazines. Ethylenepolyamine mixtures are useful.

[0048] The polyamine may also be a heterocyclic polyamine. Among theheterocyclic polyamines are aziridines, azetidines, azolidines, tetra-and dihydropyridines, pyrroles, indoles, piperidines, imidazoles, di-and tetra hydroimidazoles, piperazines, isoindoles, purines,morpholines, thiomorpholines, N-aminoalkylmorpholines,N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,N,N′-diaminoalkylpiperazines, azepines, azocines, azonines, azecines andtetra-, di- and perhydro derivatives of each of the above and mixturesof two or more of these heterocyclic amines. Useful heterocyclic aminesare the saturated 5- and 6-membered heterocyclic amines containing onlynitrogen, oxygen and/or sulfur in the hetero ring, especially thepiperidines, piperazines, thiomorpholines, morpholines, pyrrolidines,and the like. Piperidine, aminoalkyl-substituted piperidines,piperazine, aminoalky-substituted piperazines, morpholine,aminoalkyl-substituted morpholines, pyrrolidine, andaminoalkyl-substituted pyrrolidines, are useful. Usually the aminoalkylsubstituents are substituted on a nitrogen atom forming part of thehetero ring. Specific examples of such heterocyclic amines includeN-aminopropylmorpholine, N-aminoethylpiperazine, andN,N′-diaminoethylpiperazine.

[0049] The hydroxyamine (B) may be a primary, secondary or tertiaryamine. The terms “hydroxyamine” and “aminoalcohol” describe the sameclass of compounds and, therefore, can be used interchangeably. In oneembodiment, the hydroxyamine is (a) an N-(hydroxyl-substitutedhydrocarbyl) amine, (b) a hydroxyl-substituted poly(hydrocarbyloxy)analog of (a), or a mixture of (a) and (b). The hydroxyamine may bealkanolamine containing from 1 to about 40 carbon atoms, and in oneembodiment 1 to about 20 carbon atoms, and in one embodiment 1 to about10 carbon atoms.

[0050] The hydroxyamine may be a primary, secondary or tertiary alkanolamine, or a mixture of two or more thereof. These hydroxyamines may berepresented, respectively, by the formulae:

[0051] wherein each R is independently a hydrocarbyl group of one toabout eight carbon atoms or hydroxyl-substituted hydrocarbyl group oftwo to about eight carbon atoms and R′ is a divalent hydrocarbon groupof about two to about 18 carbon atoms. Typically each R is a lower alkylgroup of up to seven carbon atoms. The group —R′—OH in such formulaerepresents the hydroxyl-substituted hydrocarbyl group. R′ can be anacyclic, alicyclic or aromatic group. Typically, R′ is an acyclicstraight or branched alkylene group such as an ethylene, 1,2-propylene,1,2-butylene, 1,2-octadecylene, etc. group.

[0052] Where two R groups are present in the same molecule they can bejoined by a direct carbon-to-carbon bond or through a heteroatom (e.g.,oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ringstructure. Examples of such heterocyclic amines include N-(hydroxyllower alkyl)-morpholines, -thiomorpholines, -piperidines, -oxazolidines,-thiazolidines and the like.

[0053] The hydroxyamines may be ether N-(hydroxy-substitutedhydrocarbyl)amines. These may be hydroxyl-substitutedpoly(hydrocarbyloxy) analogs of the above-described hydroxy amines(these analogs also include hydroxyl-substituted oxyalkylene analogs).Such N-(hydroxyl-substituted hydrocarbyl) amines may be convenientlyprepared by reaction of epoxides with afore-described amines and may berepresented by the formulae:

[0054] wherein x is a number from about 2 to about 15, and R and R′ areas described above.

[0055] Polyamine analogs of these hydroxy amines, particularlyalkoxylated alkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine)may be used. Such polyamines can be made by reacting alkylene amines(e.g., ethylenediamine) with one or more alkylene oxides (e.g., ethyleneoxide, octadecene oxide) of two to about 20 carbons. Similar alkyleneoxide-alkanol amine reaction products can also be used such as theproducts made by reacting the afore-described primary, secondary ortertiary alkanol amines with ethylene, propylene or higher epoxides in a1:1 or 1:2 molar ratio. Reactant ratios and temperatures for carryingout such reactions are known to those skilled in the art.

[0056] Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl) ethylene diamine,N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl) piperazine,mono(hydroxypropyl)-substituted diethylene triamine,di(hydroxypropyl)-substituted tetraethylene pentamine, N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtained bycondensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid mono- orpolyamines are also useful.

[0057] Examples of the N-(hydroxyl-substituted hydrocarbyl) aminesinclude mono-, di-, and triethanolamine, dimethylethanolamine,diethylethanolamine, di-(3-hydroxylpropyl) amine, N-(3-hydroxylbutyl)amine, N-(4-hydroxylbutyl) amine, N,N-di-(2-hydroxylpropyl) amine,N-(2-hydroxylethyl) morpholine and its thio analog, N-(2-hydroxylethyl)cyclohexylamine, N-3-hydroxyl cyclopentyl amine, o-, m- andp-aminophenol, N-(hydroxylethyl) piperazine, N,N′-di(hydroxyl ethyl)piperazine, and the like.

[0058] Further hydroxyamines are the hydroxy-substituted primary aminesdescribed in U.S. Pat. No. 3,576,743 by the general formula

R_(a)—NH₂

[0059] wherein R_(a) is a monovalent organic group containing at leastone alcoholic hydroxy group. The total number of carbon atoms in R_(a)preferably does not exceed about 20. Hydroxy-substituted aliphaticprimary amines containing a total of up to about 10 carbon atoms areuseful. The polyhydroxy-substituted alkanol primary amines wherein thereis only one amino group present (i.e., a primary amino group) having onealkyl substituent containing up to about 10 carbon atoms and up to about6 hydroxyl groups are useful. These alkanol primary amines correspond toR_(a)-NH₂ wherein R_(a) is a mono-O or polyhydroxy-substituted alkylgroup. It is desirable that at least one of the hydroxyl groups be aprimary alcoholic hydroxyl group. Specific examples of thehydroxy-substituted primary amines include 2-amino-1-butanol,2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)-aniline,2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(betahydroxypropyl)-N′-(beta-aminoethyl)-pi-perazine,tris-(hydroxymethyl) aminomethane (also known astrismethylolaminomethane), 2-amino-1-butanol, ethanolamine,beta-(beta-hydroxyethoxy)-ethylamine, glucamine, glusoamine,4-amino-3-hydroxy-3-methyl-1-butene (which can be prepared according toprocedures known in the art by reacting isopreneoxide with ammonia),N-3(aminopropyl)-4-(2-hydroxyethyl)-piperadine,2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,N-(beta-hydroxyethyl)-1,3-diamino propane, 1,3-diamino-2-hydroxypropane,N-(beta-hydroxy ethoxyethyl)-ethylenediamine, trismethylol aminomethaneand the like.

[0060] Hydroxyalkyl alkylene polyamines having one or more hydroxyalkylsubstituents on the nitrogen atoms, are also useful. Usefulhydroxyalkyl-substituted alkylene polyamines include those in which thehydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less thaneight carbon atoms. Examples of such hydroxyalkyl-substituted polyaminesinclude N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)-piperazine,monohydroxypropyl-substituted diethylene triamine,dihydroxypropyl-substituted tetraethylene pentamine, N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as are obtained bycondensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia and condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater.

[0061] The product of the reaction between components (A) and (B) duringstep (I) of the inventive process is a first intermediate product. Thisproduct may be an ester or a partial ester when component (B) is apolyol. This product may be an amide, imide, salt, amide/salt, partialamide or mixture of two or more thereof when (B) is a polyamine. Thisproduct may be an ester, partial ester, amide, partial amide,amide/salt, imide, ester/salt, salt, or a mixture of two or more thereofwhen component (B) is a hydroxyamine, a mixture of polyol and polyamine,a mixture of polyol and hydroxyamine, or a mixture of polyamine andhydroxyamine. The salt may be an internal salt involving residues of amolecule of the acid or anhydride and the polyamine or hydroxyaminewherein one of the carboxyl groups becomes ionically bound to a nitrogenatom within the same group; or it may be an external salt wherein theionic salt group is formed with a nitrogen atom that is not part of thesame molecule. During step (I), components (A) and (B) are mixedtogether and heated at an effective temperature to form the foregoingfirst intermediate product. In one embodiment, the temperature is in therange of from about 30° C. to about 120° C., and in one embodiment fromabout 50° C. to about 90° C. The reaction time is typically from about 1to about 120 minutes, and in one embodiment about 1 to about 60 minutes.Components (A) and (B) may be dispersed or dissolved in a normallyliquid, substantially inert organic liquid solvent/diluent during thereaction. In one embodiment, components (A) and (B) are reacted inamounts sufficient to provide an equivalent ratio of (A) to (B) fromabout 3:1 to about 1:2. In one embodiment, this ratio is from about 1:1to about 1:2, and in one embodiment about 1:1.4 to about 1:1.9.

[0062] During step (II) the first intermediate product from step (I) isheated at a sufficient temperature to form a second intermediate productwith water of reaction being formed. The temperature may be in the rangeof about 130° C. to about 210° C., and in one embodiment about 135° C.to about 150° C. The reaction time is typically from about 1 to about 10hours, and in one embodiment about 1.5 to about 3 hours. When (B) is apolyol, the second intermediate product comprises one or more bisesters,triesters or low order (about 2 to about 6, and in one embodiment about2 to about 4) oligomers containing ester, or ester and acidfunctionality. When (B) is a polyamine, the second intermediate productcomprises one or more bisamides, bisimides, amide/imide, or low order(about 2 to about 6, and in one embodiment about 2 to about 4) oligomerscontaining amide, imide, amide/imide, acid and/or salt functionality.When (B) is a hydroxyamine, the second intermediate product comprisesone or more bisamides, bisesters, ester/amides or low order (about 2 toabout 6, and in one embodiment about 2 to about 4) oligomers containingester, amide, acid and/or salt functinality. When (B) is a mixture of apolyol, polyamine and/or hydroxyamine, the second intermediate productcomprises one or more of the above-mentioned products depending uponwhich polyol, polyamine and/or hydroxyamine is used. During step (II) aportion of the water of reaction is separated from the secondintermediate product using known techniques (e.g., distillation,azeotropic removal of water, molecular sieves, etc.) to provide thedesired partially dehydrated product. When component (A) is a succinicanhydride, the amount of water of reaction that is removed is generallyfrom about 0.2 to about 0.9 moles of water per equivalent of succinicanhydride, and in one embodiment about 0.3 to about 0.8 moles of waterper equivalent of succinic anhydride, and in one embodiment about 0.4 toabout 0.6 moles of water per equivalent of succinic anhydride. Whencomponent (A) is a succinic acid, the amount of water of reaction thatis removed is generally from about 1.2 to about 1.9 moles of water perequivalent of succinic acid, and in one embodiment about 1.3 to about1.8 moles of water per equivalent of succinic acid, and in oneembodiment about 1.4 to about 1.6 moles of water per equivalent ofsuccinic acid.

[0063] The inventive reaction product may be added directly to theinventive emulsion. Alternatively, it may be diluted with a normallyliquid organic diluent such as mineral oil, naphtha, benzene, or tolueneto form an additive concentrate. The normally liquid organic diluent maybe one or more of the precursors or reactants used to make the inventivereaction product, or one or more of the oils or fuels used to make theinventive emulsions described herein. The concentrate usually containsfrom about 10% to about 90% by weight of the inventive reaction productand may contain, in addition, one or more other additives known in theart or described herein.

[0064] In the following examples as well as throughout the specificationand in the claims, unless otherwise indicated, all parts and percentagesare by weight, all temperatures are in degrees Celsius (^(m)C), and allpressures are at or near atmospheric.

EXAMPLE 1

[0065] A five-liter, four-neck flask fitted with a thermocouple, anaddition funnel topped with a N₂ inlet, a Dean-Stark trap topped with awater condenser, and an overhead stirrer is charged with C₁₈₋₃₀ alkenylsuccinic anhydride (1740.8 g, 3.71 mol). The contents of the flask arestirred and heated to 64° C. Diethanolamine (590 g, 5.62 mol) is addedvia the addition funnel over 35 minutes. The mixture undergoes anexothem to 105° C. The mixture is heated to 140° C. over 20 minutes andheld at that temperature for 2 hours and 40 minutes. Water of reaction(24 g) is removed. The product has a TAN of 53 mg of KOH/g and a TBN of53.7 mg of KOH/g.

EXAMPLE 2

[0066] A five-liter, four-neck flask fitted with a thermocouple, anaddition funnel topped with a N₂ inlet, a Dean-Stark trap topped with awater condenser, and an overhead stirrer is charged with C₁₈₋₃₀ alkenylsuccinic anhydride (1715 g, 3.66 mol). The contents of the flask arestirred and heated to 50° C. Diethanolamine (653 g, 6.22 mol) is addedvia the addition funnel over 25 minutes (reaction undergoes an exothermto 120° C.). The mixture is heated to 140° C. and held at thattemperature for 5 hours. Water of reaction (35 g) is removed. Theproduct has a TAN of 37 mg of KOH/g, and a TBN of 57 mg of KOH/g.

EXAMPLE 3

[0067] A five-liter, four-neck flask fitted with a thermocouple, anaddition funnel topped with a N₂ inlet, a Dean-Stark trap topped with awater condenser, and an overhead stirrer is charged with C18.30 alkenylsuccinic anhydride (2133 g, 4.55 mol). The contents of the flask arestirred and heated to 64° C. Glycerol (628 g, 6.83 mol) is added via theaddition funnel over 20-25 minutes. The mixture is heated to 150° C.over 40 minutes. The temperature of the reaction mixture is increasedfrom 150° C. to 170° C. over a period of 5 hours and maintained at 170°C. for an additional hour. Water of reaction (45 g) is removed. Theproduct has a TAN of 38 mg of KOH/g.

EXAMPLE 4

[0068] A three-liter, four-neck flask fitted with an overhead stirrer, athermocouple, an addition funnel topped with a N₂ inlet, and aDean-Stark trap topped with a condenser is charged with C₁₈₋₃₀ alkenylsuccinic anhydride (1360.6 g, 2.90 mol). The contents of the flask arestirred and heated to 63° C. Diethanolamine (406 g, 3.87 mol) is addedvia the addition funnel over 27 minutes. During the addition, thereaction mixture undergoes an exotherm to 114° C. The temperature isincreased to 140° C. over 15 minutes by external heating, and maintainedat that temperature for 45 minutes. Water of reaction (18 g) is removed.The mixture is cooled to room temperature. The TAN of the final productis 60.7 mg of KOH/g.

EXAMPLE 5

[0069] A two-liter, four-neck flask equipped with a stopcock drain, anoverhead stirrer, a thermocouple, an addition funnel topped with a N₂inlet, and a Dean-Stark trap topped with a water condenser, is chargedwith C₁₈₋₃₀ alkenyl succinic anhydride (1050.3 g, 2.24 mol). Thecontents of the flask are heated to 60° C. Triethanolamine (158.7 g,1.06 mol) and glycerol (293.9 g, 3.19 mol) are added sequentially over a30-minute period. During the triethanolamine addition, the reactionmixture undergoes an exotherm to 90° C. Upon completion of glyceroladdition, the reaction, mixture is stirred and heated to 140° C., andmaintained at that temperature for 5 hours to provide the final productwhich is in the form is a viscous brown liquid. Water of reaction (25 g)is removed. The product has a TAN of 29.3 mg of KOH/g, a TBN of 39.8 mgof KOH/g, and a nitrogen content of 0.98% by weight.

EXAMPLE 6

[0070] A one-liter, four-neck flask fitted with a thermocouple, anaddition funnel topped with a N₂ inlet, a Dean-Stark trap topped with awater condenser, and an overhead stirrer is charged with C18-30 alkenylsuccinic anhydride (251.4 g, 0.57 mol) and a mixture of C16-C18 alphaolefins (140.3 g). The contents of the flask are stirred and heated to90° C. A polyamine bottoms product corresponding predominately totetraethylene pentamine (29.6 g, 0.71 mol), is added dropwise via theaddition funnel. The mixture undergoes an exothem to 110^(m)C. Themixture is maintained at 100° C. for 3.5 hours. Water of reaction (3.15g) is removed. The product has a TAN of 49.7 mg of KOH/g.

EXAMPLE 7

[0071] A one-liter, four-neck flask fitted with a thermocouple, anaddition funnel topped with a N₂ inlet, a Dean-Stark trap topped with awater condenser, and an overhead stirrer is charged with C₁₈₋₃₀ alkenylsuccinic anhydride (315.6 g, 0.72 mol) and a mixture of C₁₆-C₁₈ alphaolefins (167.0 g). The contents of the flask are stirred and heated to90 C. A polyamine bottoms product corresponding predominately totetraethylene pentamine (30 g, 0.72 mol) is added via the additionfunnel over 10 minutes. The mixture undergoes an exothem to 120 C. Themixture is maintained at 100° C. with stirring for 3.5 hours. Water ofreaction (4.0 g) is removed. The product has a TAN of 55.4 mg of KOH/g.

EXAMPLE 8

[0072] A one-pint jar is charged with propylene tetramer substitutedsuccinic anhydride (267 g) and diethanol amine (63 g) and heated to 160°C. with stirring over a period of 30 minutes. A nitrogen sparge at arate of 5 standard cubic feet per hour is used during the heatingperiod. Water of reaction is removed. The color of the liquid mixturechanges from lemon-yellow to orange-amber.

EXAMPLE 9

[0073] A one-liter, five-neck flask is charged with propylene tetramersubstituted succinic anhydride (296 g), glycerine (96 g) and triethanolamine (176 g). The mixture is heated to 110° C. with stirring and anitrogen purge. The temperature is maintained at 110° C. for 1 hour,then heated to 230° C. over a period of 3 hours. Water (23 g) isremoved. The mixture is cooled to 100° C. and filtered.

EXAMPLE 10

[0074] A two-liter, three-neck flask is charged with propylene tetramersubstituted succinic anhydride (592 g), glycerine (384 g), toluene (300ml) and p-CH₃C₆H₄SO₃.H₂O (10 g). The mixture is heated to reflux withstirring and a nitrogen purge (0.05 standard cubic feet per hour) andheld at reflux for 3 hours. The temperature increases from 12° C. to135° C. during this period. Water (40 g) and toluene (150 ml) areremoved. The temperature is cooled to 90 C and a 50% aqueous solution ofNaOH (4.3 g) is added dropwise with stirring. The mixture is stirred for15 minutes. Toluene is stripped from the mixture at 110^(m)C and 15mmHg. The mixture is filtered. Emulsions The inventive partiallydehydrated reaction products are useful as emulsifiers in emulsions.These emulsions are comprised of an organic phase, an aqueous phase andan emulsifying amount of inventive reaction product. The emulsions maybe water-in-oil emulsions or oil-in-water emulsions. The term“oil-in-water” emulsion (abbreviated “o/w” emulsion) refers to emulsionswherein the continuous phase is aqueous and the discontinuous phase isorganic, the discontinuous organic phase being dispersed in thecontinuous aqueous phase. The term “water-in-oil” emulsion (abbreviated“w/o” emulsion) refers to emulsions wherein the continuous phase isorganic and the discontinuous phase is aqueous, the discontinuousaqueous phase being dispersed in the continuous organic phase. Theemulsions may contain from about 0.5% to about 99.5% by weight aqueousphase and from about 99.5% to about 0.5% by weight organic phase. Theemulsions may contain from about 10% to about 90% by weight, and in oneembodiment about 20% to about 80% by weight aqueous phase; and fromabout 90% to about 10%, and in one embodiment about 80% to about 20%organic phase. In one embodiment, the emulsion is water-in-oil emulsion(sometimes referred to as an “invert” emulsion) and the weight ratio ofthe aqueous phase to the organic phase ranges from about 1:1 to about99.5:1, and in one embodiment about 2:1 to about 99:1. In oneembodiment, the emulsion is a high internal phase emulsion and theweight ratio of the aqueous phase to the organic phase is at least about4:1, and in one embodiment at least about 5:1, and one embodiment atleast about 8:1.

[0075] The organic phase of the emulsions may be based on a widelydiverse group of oils, including natural oils, synthetic oils, andmixtures thereof. The natural oils include animal oils and vegetableoils (e.g., castor oil, lard oil) as well as mineral oils such as liquidpetroleum oils and solvent treated or acid-treated mineral oils of theparaffinic, naphthenic or mixed paraffinic-naphthenic types. Oilsderived from coal or shale are also useful. Synthetic oils includehydrocarbon oils and halo-substituted hydrocarbon oils such aspolymerized and interpolymerized olefins (e.g., polybutylenes,polypropylenes, propylene-isobutylene copolymers, chlorinatedpolybutylenes, etc.); poly(1-hexenes), poly-(1-octenes),poly(1-decenes), etc. and mixtures thereof; alkyl-benzenes (e.g.,dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers andalkylated diphenyl sulfides and the derivatives, analogs and homologsthereof and the like.

[0076] Alkylene oxide polymers and interpolymers and derivatives thereofwhere the terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another class of known synthetic oilsthat can be used. These are exemplified by the oils prepared throughpolymerization of ethylene oxide or propylene oxide, the alkyl and arylethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropyleneglycol ether having an average molecular weight of about 1000, diphenylether of polyethylene glycol having a molecular weight of about500-1000, diethyl ether of polypropylene glycol having a molecularweight of about 1000-1500, etc.) or mono- and polycarboxylic estersthereof, for example, the acetic acid esters, mixed C₃₋₈ fatty acidesters, or the C₁₃Oxo acid diester of tetraethylene glycol.

[0077] Another suitable class of synthetic oils that can be usedcomprises the esters of dicarboxylic acids (e.g., phthalic acid,succinic acid, alkyl succinic acids, alkenyl succinic acids, maleicacid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipicacid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenylmalonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol,hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol,diethylene glycol monoether, propylene glycol, etc.) Specific examplesof these esters include dibutyl adipate, di(2-ethylhexyl) sebacate,di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecylazelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the2-ethylhexyl diester of linoleic acid dimer, the complex ester formed byreacting one mole of sebacic acid with two moles of tetraethylene glycoland two moles of 2-ethylhexanoic acid and the like.

[0078] Esters useful as synthetic oils also include those made from C₅to C₁₂ monocarboxylic acids and polyols and polyol ethers such asneopentyl glycol, trimethylol propane, pentaerythritol,dipentaerythritol, tripentaerythritol, etc.

[0079] Silicon-based oils such as the polyalkyl-, polyaryl-,polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils compriseanother useful class of synthetic lubricants (e.g., tetraethyl silicate,tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butylphenyl) silicate,hexyl-(4-methyl-2pentoxy)disiloxane, poly(methyl) siloxanes,poly(methylphenyl)siloxanes, etc.). Other synthetic oils include liquidesters of phosphorus-containing acids (e.g., tricresyl phosphate,trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.),polymeric tetrahydrofurans and the like.

[0080] Unrefined, refined and rerefined oils, either natural orsynthetic (as well as mixtures of two or more of any of these) of thetype disclosed hereinabove can be used. Unrefined oils are thoseobtained directly from a natural or synthetic source without furtherpurification treatment. For example, a shale oil obtained directly fromretorting operations, a petroleum oil obtained directly from primarydistillation or ester oil obtained directly from an esterificationprocess and used without further treatment would be an unrefined oil.Refined oils are similar to the unrefined oils except they have beenfurther treated in one or more purification steps to improve one or moreproperties. Many such purification techniques are known to those skilledin the art such as solvent extraction, secondary distillation, acid orbase extraction, filtration, percolation, etc. Rerefined oils areobtained by processes similar to those used to obtain refined oilsapplied to refined oils which have been already used in service. Suchrerefined oils are also known as reclaimed or reprocessed oils and oftenare additionally processed by techniques directed to removal of spentadditives and oil breakdown products.

[0081] As indicated above, the inventive reaction products are useful inmaking emulsions for a wide variety of applications. These includeexplosive emulsions, emulsion fertilizers, water-blended fuels,lubricants and/or functional fluids, acidizing fluids, and the like.

[0082] Explosives Emulsions

[0083] The explosive emulsions include water-in-oil emulsions whichcomprise a discontinuous oxidizer phase comprising water and at leastone oxygen-supplying component, a continuous organic phase comprising atleast one carbonaceous fuel, and an emulsifying amount of the inventivereaction product.

[0084] The continuous organic phase may be present at a level of atleast about 2% by weight, and in one embodiment in the range of fromabout 2% to about 15% by weight, and in one embodiment from about 3.5%to about 8% by weight based on the total weight of explosive emulsion.The discontinuous oxidizer phase may be present at a level of at leastabout 85% by weight, and in one embodiment at a level in the range offrom about 85% to about 98% by weight, and in one embodiment about 92%to about 96.5% by weight based on the total weight of the explosiveemulsion. The inventive reaction product may be present at a level inthe range from about 5% to about 50% by weight, and in one embodimentfrom about 10% to about 20% by weight based on the total weight of theorganic phase. The oxygen-supplying component may be present at thelevel in the range of about 70% to about 95% by weight, and in oneembodiment about 85% to about 92% by weight, and in one embodiment from87% to about 90% by weight based on the total weight of the oxidizerphase. The water may be present at a level in the range of about 5% toabout 30% by weight, and in one embodiment about 8% to about 15% byweight, and in one embodiment about 10% to about 13% by weight based onthe weight of the oxidizer phase.

[0085] The carbonaceous fuels that are useful in these explosiveemulsions include most hydrocarbons, for example, paraffinic, olefinic,naphthenic, aromatic, saturated or unsaturated hydrocarbons, and may bein the form of an oil or a wax or a mixture thereof. In general, thecarbonaceous fuel is a water-immiscible, emulsifiable hydrocarbon thatis either liquid or liquefiable at a temperature of up to about 95° C.,and in one embodiment between about 40° C. and about 75° C. Any of thenatural or synthetic oils discussed above may be used as thecarbonaceous fuel.

[0086] Examples of useful oils include a white mineral oil availablefrom Witco Chemical Company under the trade designation KAYDOL; a whitemineral oil available from Shell under the trade designation ONDINA; anda mineral oil available from Pennzoil under the trade designationN-750-HT. Diesel fuel (e.g., Grade No. 2-D as specified in ASTM-D975)can be used as the oil.

[0087] The carbonaceous fuel may be any wax having melting point of atleast about 25° C., such as petrolatum wax, microcrystalline wax, andparaffin wax, mineral waxes such as ozocertie and montan wax, animalwaxes such as spermacetic wax, and insect waxes such as beeswax andChinese wax. Useful waxes include waxes identified by the tradedesignation MOBILWAX 57 which is available from Mobil Oil Corporation;D02764 which is a blended wax available from Astor Chemical Ltd.; andVYBAR which is available from Petrolite Corporation. Useful waxes areblends of microcrystalline waxes and paraffin.

[0088] In one embodiment, the carbonaceous fuel includes a combinationof a wax and an oil. In this embodiment, the wax content may be at leastabout 25% by weight, and in one embodiment from about 25% to about 90%by weight of the organic phase; and the oil content may be at leastabout 10%, and in one embodiment from about 10% to about 75% by weightof the organic phase.

[0089] The explosive emulsions may also contain up to about 15% byweight of an auxiliary fuel, such as aluminum, aluminum alloys,magnesium, and the like. Particulate aluminum is a preferred auxiliaryfuel.

[0090] The oxygen-supplying component may be an inorganic oxidizer saltsuch as ammonium, alkali or alkali or alkaline earth metal nitrate,chlorate or perchlorate. Examples include ammonium nitrate, sodiumnitrate, calcium nitrate, ammonium chlorate, sodium perchlorate andammonium perchlorate. Ammonium nitrate is especially useful. Mixtures ofammonium nitrate and sodium or calcium nitrate are also useful. In oneembodiment, the inorganic oxidizer salt comprises principally ammoniumnitrate, although up to about 25% by weight of the oxidizer phase maycomprise either another inorganic nitrate (e.g., alkali or alkalineearth metal nitrate) or an inorganic perchlorate (e.g., ammoniumperchlorate or an alkali or alkaline earth metal perchlorate) or amixture thereof.

[0091] In one embodiment, closed-cell, void-containing materials areused as sensitizing components. The term “closed-cell, void-containingmaterial” is used herein to mean any particulate material whichcomprises closed cell, hollow cavities. Each particle of the materialcan contain one or more closed cells, and the cells can contain a gas,such as air, or can be evacuated or partially evacuated. In oneembodiment, sufficient closed cell void containing material is used toyield a density in the resulting emulsion of from about 0.8 to about1.35 g/cc. In general, the explosive emulsions may contain up to about15% by weight, and in one embodiment about 0.25% to about 15% by weightof the closed cell void containing material. Useful closed cell voidcontaining materials include discrete glass spheres having a particlesize within the range of about 10 to about 175 microns. In general, thebulk density of such particles may be within the range of about 0.1 toabout 0.4 g/cc. Useful glass microbubbles or microballoons which can beused are the microbubbles sold by 3M Company and which have a particlesize distribution in the range of from about 10 to about 160 microns anda nominal size in the range of about 60 to 70 microns, and densities inthe range of from about 0.1 to about 0.4 g/cc; these includemicroballoons distributed under the trade designation C15/250. Otheruseful glass microbubbles are sold under the trade designation ofECCOSPHERES by Emerson & Cumming, Inc., and generally have a particlesize range from about 44 to about 175 microns and a bulk density ofabout 0.15 to about 0.4 g/cc. Other suitable microbubbles include theinorganic microspheres sold under the trade designation of Q-CEL byPhiladelphia Quartz Company. The closed cell void containing materialmay be made of inert or reducing materials. For example,phenol-formaldehyde microbubbles can be utilized. If thephenol-formaldehyde microbubbles are utilized, the microbubblesthemselves are a fuel component for the explosive. Another closed cellvoid containing material which may be used are saran microspheres soldby Dow Chemical Company. The saran microspheres have a diameter of about30 microns and a particle density of about 0.032 g/cc.

[0092] Gas bubbles which are generated in-situ by adding to thecomposition and distributing therein a gas-generating material such as,for example, an aqueous solution of sodium nitrite, can be used tosensitize the explosive emulsions. Other suitable sensitizing componentswhich may be employed alone or in addition to the foregoing includeinsoluble particulate solid self-explosives such as, for example,grained or flaked TNT, DNT, RDX and the like and water-soluble and/orhydrocarbon-soluble organic sensitizers such as, for example, aminenitrates, alkanolamine nitrates, hydroxyalkyl nitrates, and the like.The explosives emulsions may be formulated for a wide range ofapplications. Any combination of sensitizing components may be selectedin order to provide an explosive composition of virtually any desireddensity, weight-strength or critical diameter. The quantity of solidself-explosive ingredients and of water-soluble and/orhydrocarbon-soluble organic sensitizers may comprise up to about 40% byweight of the total explosive emulsion. The volume of the occluded gascomponent may comprise up to about 50% of the volume of the totalexplosive emulsion.

[0093] Optional additional materials may be incorporated in theexplosive emulsions in order to further improve sensitivity, density,strength, rheology and cost of the final explosive. Typical of materialsfound useful as optional include, for example, particulate non-metalfuels such as sulfur, gilsonite and the like, particulate inertmaterials such as sodium chloride, barium sulphate and the like, waterphase or hydrocarbon phase thickeners such as guar gum, polyacrylamide,carboxymethyl or ethyl cellulose, biopolymers, starches, elastomericmaterials, and the like, crosslinkers for the thickeners such aspotassium pyroantimonate and the like, buffers or pH controllers such assodium borate, zinc nitrate and the like, crystals habit modifiers suchas alkyl naphthalene sodium sulphonate and the like, liquid phaseextenders such as formamide, ethylene glycol and the like and bulkingagents and additives of common use in the explosives art. The quantitiesof optional additional materials used may comprise up to about 50% byweight of the total explosive emulsion.

[0094] A useful method for making the explosive emulsions comprises thesteps of (1) mixing water, inorganic oxidizer salts (e.g., ammoniumnitrate) and, in certain cases, some of the supplemental water-solublecompounds, in a first premix, (2) mixing the carbonaceous fuel, theemulsifying reaction product of the invention and any other optionaloil-soluble compounds in a second premix and (3) adding the first premixto the second premix in a suitable mixing apparatus, to form awater-in-oil emulsion. The first premix may be heated until all thesalts are completely dissolved. The solution may be filtered if neededin order to remove any insoluble residue. The second premix may be alsoheated to liquefy the ingredients. Any type of apparatus capable ofeither low or high shear mixing can be used to prepare thesewater-in-oil emulsions. Closed-cell void containing materials,gas-generating materials, solid self-explosive ingredients such asparticulate TNT, solid fuels such as aluminum or sulfur, inert materialssuch as barytes or sodium chloride, undissolved solid oxidizer salts andother optional materials, if employed, may be added to the emulsion andsimply blended until homogeneously dispersed throughout the composition.

[0095] The explosive emulsions may be prepared by adding the secondpremix liquefied organic solution phase to the first premix hot aqueoussolution with sufficient stirring to invert the phases. However, thismethod usually requires substantially more energy to obtain the desireddispersion than does the preferred reverse procedure. Alternatively,these explosive emulsions are particularly adaptable to preparation by acontinuous mixing process where the two separately prepared liquidphases are pumped through a mixing device wherein they are combined andemulsified.

[0096] Illustrative explosive emulsions are provided in Table I. InTable I all numerical values are in parts by weight. TABLE I A B Productof Example 1 1 — Product of Example 7 — 1 Mineral Oil 6 6 Water 14.614.6 Ammonium nitrate 77.2 77.2

[0097] Emulsion Fertilizers

[0098] The emulsion fertilizers are water-in-oil emulsions which employthe inventive reaction product as an emulsifier. These emulsions arecomprised of a discontinuous aqueous fertilizer phase comprising atleast one water soluble fertilizer component, a continuous organic phasecomprising at least one oil, and an emulsifying amount of the inventivereaction product. The emulsion fertilizers share some characteristicswith the foregoing explosive emulsions. For example, both arewater-in-oil emulsions, and both may include ammonium nitrate as acomponent. However, the emulsion fertilizers are different from theexplosive emulsions in that the ability to detonate is a necessaryfeature of the emulsion explosives and is an undesirable characteristicsof an emulsion fertilizer. There are several methods which may be usedto assure that emulsion fertilizer is non-explosive. It is important toavoid materials which may act as sensitizers in emulsions explosives.These explosive sensitive include glass or resin microspheres or othergas containing particles, self explosive materials such as TNT, DNT, RDXand the like and various organic nitrates. Emulsion explosives maycontain particulate oxygen supplying salts such as potassiumperchlorate. Extra quantities of oxygen supply salts are to be avoidedin fertilizer compositions. Ammonium nitrate is commonly used inemulsion explosives. It also a valuable fertilizer ingredient. Urea maybe used to replace some of the ammonium nitrate. Such replacementresults in an emulsion which is less explosive. The inclusion of otherfertilizers components which are not oxidizing salts, such as phosphatestend to make the emulsions less explosive. By use of the one orcombinations of the methods discussed above-the emulsion fertilizers ofthe invention may be rendered non-explosive.

[0099] The water soluble fertilizer components include the majorfertilizer components which supply nitrogen, potassium and phosphorous.Optionally, various components to supply specialized nutrients may beincluded. Thus, if a particular soil is deficient in a trace element auseable form of this element could be included in the emulsion. Examplesof such trace elements include boron, iron, manganese, sulfur, zinc,copper and molybdenum. These materials may be used in the form of theirsalts, or in other suitable form. If the salts are soluble, they may beincorporated in the aqueous phase, and if insoluble, they may besupplied by organic material such as urea, guanidine, and their salts,as well as by inorganic materials such as ammonium nitrate, alkali metalnitrates, and alkaline earth nitrates. Potassium may be supplied bypotassium salts such as carbonate, chloride, nitrate, phosphates,pyrophosphate, and sulfate. Phosphorous may be supplied by alkali andalkaline earth metal phosphate salts.

[0100] The continuous organic phase, that is, the oil phase that isuseful in the emulsion fertilizers of the invention may include oilsfrom a variety of sources, including natural and synthetic oils andmixtures thereof similar to those discussed above.

[0101] The biodegradability of the oil phase is important in fertilizercompositions. Thus the more biodegradable mineral oils are favored overthe heavier less biodegradable oils. Vegetable oils are favored becauseof their biodegradability and because of their ready availability.Usable vegetable oils include babbasu, palm, castor, olive, peanut,rapeseed, corn, sesame, coconut, cottonseed, soybean, linseed, sunflowerand safflower. It has been found that vegetable oils in general formemulsions which release the fertilizer components more quickly thanemulsions prepared from mineral oils. Accordingly, the type of oilemployed in preparing the emulsion fertilizer may also be used tocontrol the rate of release of the fertilizer components. Pure vegetableoil, or mixtures of vegetable oil and mineral oils may be used to obtainthe exact rate of release desired.

[0102] The continuous organic phase may be present at a level of atleast about 2% by weight, and in one embodiment in the range of fromabout 2% to about 15% by weight, and in one embodiment in the range offrom about 3.5% to about 8% by weight based on the total weight offertilizer emulsion. The discontinuous fertilizer phase may be presentat a level of at least about 85% by weight, and in one embodiment at alevel in the range of from about 85% to about 98% by weight, and in oneembodiment from about 92% to about 96.5% by weight based on the totalweight of said fertilizer emulsion. The inventive reaction product maybe present at a level in the range of from about 4% to about 40% byweight, and in one embodiment from about 12% to about 20% by weightbased on the total weight of the organic phase. The fertilizer componentor components may be present at a level in the range of from about 70%to about 95% by weight, and in one embodiment from about 85% to about92% by weight, and in one embodiment from about 87% to about 90% byweight based on the total weight of the aqueous phase. The water may bepresent at a level in the range of about 5% to about 30% by weight, andin one embodiment about 8% to about 15% by weight, and in one embodimentabout 10% to about 13% by weight based on the weight of the aqueousphase.

[0103] The emulsion fertilizers may be prepared by dissolving theinventive reaction product in the oil phase, and adding the aqueousphase with stirring. The aqueous phase is prepared by dissolving thefertilizer components in water. Only moderate shear mixing is required.Both stirred and static mixers are useable in preparing the emulsionfertilizers.

[0104] The fertilizer composition may include solid fertilizercomponents suspended in the emulsion. The suspended components mayinclude any of the water soluble fertilizer components noted above.Since these components are suspended in the emulsion, but are notprotected by the continuous oil phase, they will be released ratherquickly. By this means, a fertilizer may be prepared which provides forearly release of some components, and delayed release of the rest. Forexample, a fertilizer could be prepared which releases some nitrogenearly and delays the rest. Such a fertilizer could provide a fertilizerdosage in one application which would require two applications ofconventional fertilizer. In addition, soil conditioning components,which are insoluble in water could be suspended in the fertilizeremulsion. For example powdered limestone could be suspended in thefertilizer. The limestone would serve to correct the pH balance of acidsoils.

[0105] Illustrative emulsion fertilizers are provided in Table II. InTable II all numerical values are in parts by weight. TABLE II A B CProduct of Example 1 1 — — Product of Example 5 — 1 — Product of Example7 — — 1 Durasyn 162 (product of 3 3 3 Durasyn identified as a poly alphaolefin) Vegetable Oil 1 1 1 Water 4.75 4.75 4.75 Ammonium nitrate 47.2747.27 47.27 Urea 42.6 42.6 42.6

[0106] Water-Blended Fuels

[0107] The inventive reaction products are useful as emulsifiers inmaking water-blended fuels (sometimes referred to as aqueous hydrocarbonfuels). These water-blended fuels are comprised of a continuous phase ofa normally liquid hydrocarbon fuel, a discontinuous aqueous phase, andan emulsifying amount of the inventive reaction product.

[0108] The water used in making these water-blended fuels may be takenfrom any convenient source. In one embodiment, the water is deionizedprior to being mixed with the normally liquid hydrocarbon fuel. In oneembodiment, the water is purified using reverse osmosis or distillation.The water may be present in the water-blended fuel at a concentration ofabout 5 to about 40% by weight, and in one embodiment about 10 to about30% being weight, and in one embodiment about 15 to about 25% by weight.

[0109] The normally liquid hydrocarbon fuel may be a hydrocarbonaceouspetroleum distillate fuel such as motor gasoline as defined by ASTMSpecification D439 or diesel fuel or fuel oil as defined by ASTMSpecification D396. Normally liquid hydrocarbon fuels comprisingnon-hydrocarbonaceous materials such as alcohols, ethers, organo-nitrocompounds and the like (e.g., methanol, ethanol, diethyl ether, methylethyl ether, nitromethane) are also within the scope of this inventionas are liquid fuels derived from vegetable or mineral sources such ascorn, alfalfa, shale and coal. Normally liquid hydrocarbon fuels whichare mixtures of one or more hydrocarbonaceous fuels and one or morenon-hydrocarbonaceous materials are also contemplated. Examples of suchmixtures are combinations of gasoline and ethanol and of diesel fuel andether.

[0110] In one embodiment, the normally liquid hydrocarbon fuel isgasoline, that is, a mixture of hydrocarbons having an ASTM distillationrange from about 60° C. at the 10% distillation point to about 205° C.at the 90% distillation point.

[0111] The diesel fuels that are useful with this invention can be anydiesel fuel. These diesel fuels typically have a 90% point distillationtemperature in the range of about 300° C. to about 390° C., and in oneembodiment about 330° C. to about 350° C. The viscosity for these fuelstypically ranges from about 1.3 to about 24 centistokes at 40° C. Thediesel fuels can be classified as any of Grade Nos. 1-D, 2-D or 4-D asspecified in ASTM D975. These diesel fuels may contain alcohols andesters. In one embodiment the diesel fuel has a sulfur content of up toabout 0.05% by weight (low-sulfur diesel fuel) as determined by the testmethod specified in ASTM D2622-87.

[0112] The normally liquid hydrocarbon fuel is present in thewater-blended fuel compositions of the invention at a concentration ofabout 50% to about 95% by weight, and in one embodiment about 60% toabout 95% by weight, and in one embodiment about 65% to about 85% byweight, and in one embodiment about 70% to about 80% by weight.

[0113] The inventive reaction product may be present in thewater-blended fuel at a concentration in the range of about 0.05% toabout 15% by weight, and in one embodiment about 0.05% to about 10%, andin one embodiment about 0.05% to about 5%, and in one embodiment about0.1% to about 2% by weight.

[0114] In addition to the inventive reaction product, other additiveswhich are well known to those of skill in the art may be used. Theseinclude antiknock agents such as tetraalkyl lead compounds, leadscavengers such as haloalkanes (e.g., ethylene dichloride and ethylenedibromide), ashless dispersants, deposit preventers or modifiers such astriaryl phosphates, dyes, cetane improvers, anti-oxidants such as2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors such as alkylatedsuccinic acids and anhydrides, bacteriostatic agents, gum inhibitors,metal deactivators, demulsifiers, upper cylinder lubricants andanti-icing agents. Water-soluble salts capable of forming positive andnegative ions in an aqueous solution that do not interfere with theother additives or the hydrocarbon fuel may be added. These includeorganic amine nitrates, azides, and nitro compounds. Also included arealkali and alkaline earth metal carbonates, sulfates, sulfides,sulfonates, and the like. Particulary useful are the amine or ammoniumsalts (e.g., ammonium nitrate). These additives may be used atconcentrations of up to about 1% by weight based on the total weight ofthe water-blended fuel compositions, and in one embodiment about 0.01 toabout 1% by weight.

[0115] In one embodiment, the water-blended fuel compositions contain anantifreeze agent. The antifreeze agent is typically an alcohol. Examplesinclude ethylene glycol, propylene glycol, methanol, ethanol, andmixtures thereof. Methanol, ethanol and ethylene glycol are particularlyuseful. The antifreeze agent is typically used at a concentrationsufficient to prevent freezing of the water used in the inventivecomposition. The concentration is therefore dependent upon thetemperature at which the process is operated or the temperature at whichthe fuel is stored or used. In one embodiment, the concentration is at alevel of up to about 10% by weight, and in one embodiment about 0.1% toabout 10% by weight of the water-blended fuel composition, and in oneembodiment about 1% to about 5% by weight.

[0116] The water-blended fuels may be prepared by dissolving theinventive reaction product as well as one or more of the other optionaladditives referred to above in the fuel phase, and then adding theaqueous phase using high-shear mixing. The antifreeze agent, if used, istypically added to the aqueous phase prior to being blended with thefuel.

[0117] Illustrative water-blended fuels are provided in Table III. InTable III all numerical values are in parts by weight. TABLE III A B CProduct of Example 1 0.8 — — Product of Example 3 — 0.8 — Product ofExample 7 — — 0.8 Diesel Fuel 79.6 79.6 79.6 Water 19.6 19.6 19.6

[0118] Lubricants and/or Functional Fluids

[0119] The emulsions of the invention may be used as lubricants and/orfunctional fluids. These emulsions are typically comprised of an oilphase an aqueous phase, an emulsifying amount of the inventive reactionproduct, and at least one functional additive. The emulsion may be awater-in-oil emulsion or an oil-in-water emulsion. The lubricants and/orfunctional fluids include hydraulic fluids, metal working fluids,cutting fluids and the like. These emulsions may contain from about 0.5%to about 70% by weight, and in one embodiment about 2% to about 35% byweight oil; about 30% to about 99.5% by weight, and in one embodimentabout 65% to about 98% by weight water; about 0.1% to about 10% byweight, and in one embodiment about 0.1% to about 5% by weight of theinventive reaction product; and about 0.001% to about 5% by weight, andin one embodiment about 0.001% to about 2% by weight of at least onefunctional additive.

[0120] The functional additives that are useful include extreme pressureagents, anti-wear agents, load-carrying agents, dispersants, frictionmodifiers, lubricity agents, anti-slip agents, film formers, frictionmodifiers, and mixtures of two or more thereof. As is well known, suchadditives may function in two or more of the above-mentioned ways; forexample, extreme pressure agents often function as load-carrying agents.

[0121] These functional additives may include certain solid lubricantssuch as graphite, molybdenum disulfide and polytetrafluoroethylene andrelated solid polymers.

[0122] These functional additives may include frictional polymerformers. Briefly, these are potential polymer forming materials whichare dispersed in a liquid carrier at low concentration and whichpolymerize at rubbing or contacting surfaces to form protectivepolymeric films on the surfaces. The polymerizations are believed toresult from the heat generated by the rubbing and, possibly, fromcatalytic and/or chemical action of the freshly exposed surface. Aspecific example of such materials is dilinoleic acid and ethyleneglycol combinations which can form a polyester frictional polymer film.These materials are known to the art and descriptions of them are found,for example, in the journal “Wear”, Volume 26, pages 369-392, and GermanPublished Patent Application 2,339,065. These disclosures are herebyincorporated by reference for their discussions of frictional polymerformers.

[0123] The functional additives may include metal or amine salts oforgano sulfur, phosphorus, boron or carboxylic acids. Typically suchsalts are of carboxylic acids of 1 to about 22 carbon atoms includingboth aromatic and aliphatic acids; sulfur acids such as alkyl andaromatic sulfonic acids and the like; phosphorus acids such asphosphoric acid, phosphorus acid, phosphinic acid, acid phosphate estersand analogous sulfur homologs such as the thiophosphoric anddithiophosphoric acid and related acid esters; boron acids include boricacid, acid borates and the like. Useful functional additives alsoinclude metal dithiocarbamates such as molybdenum and antimonydithiocarbamates; as well as dibutyl tin sulfide, tributyl tin oxide,phosphates and phosphites; borate amine salts, chlorinated waxes;trialkyl tin oxide, molybdenum phosphates, and chlorinated waxes.

[0124] Many useful functional additives are known to the art. Forexample, descriptions of additives useful in the inventive emulsions maybe found in “Advances in Petroleum Chemistry and Refining”, Volume 8,edited by John J. McKetta, Interscience Publishers, New York, 1963,pages 31-38 inclusive; Kirk-Othmer “Encyclopedia of ChemicalTechnology”, Volume 12, Second Edition, Interscience Publishers, NewYork, 1967, page 575 et seq.; “Lubricant Additives” by M. W. Ranney,Noyes Data Corporation, Park Ridge, N.J., U.S.A., 1973; and “LubricantAdditives” by C. V. Smalheer and R. K. Smith, The Lezius-Hiles Co.,Cleveland, Ohio, U.S.A. These references are hereby incorporated byreference for their disclosures of functional additives useful in theemulsions of this invention.

[0125] In one embodiment, the functional additive is a sulfur orchloro-sulfur extreme pressure agent, known to be useful in oil-basesystems. Such materials include chlorinated aliphatic hydrocarbons, suchas chlorinated wax; organic sulfides and polysulfides, such asbenzyl-disulfide, bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide,sulfurized sperm oil, sulfurized methyl ester of oleic acid, sulfurizedalkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurizedDiels-Alder adducts; phosphosulfurized hydrocarbons, such as thereaction product of phosphorus sulfide with turpentine or methyl oleate;phosphorus esters such as the dihydrocarbon and trihydrocarbonphosphites, i.e., dibutyl phosphite, diheptyl phosphite, dicyclohexylphosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecylphosphite, distearyl phosphite and polypropylene substituted phenolphosphite; metal thiocarbamates, such as zinc dioctyidithiocarbamate andbarium heptylphenol dithiocarbamate; and Group II metal salts of aphosphorodithioic acid, such as zinc dicyclohexyl phosphorodithioate.

[0126] The functional additive may be a film former such as a syntheticor natural latex or emulsion thereof in water. Such latexes includenatural rubber latexes and polystyrene butadienes synthetic latex.

[0127] The functional additive may be an anti-chatter or anti-squawkagent. Examples of the former are the amide metal dithiophosphatecombinations such as disclosed in West German Patent 1,109,302; aminesalt-azomethene combinations such as disclosed in British PatentSpecification 893,977; or amine dithiophosphate such as disclosed inU.S. Pat. No. 3,002,014. Examples of anti-squawk agents areN-acyl-sarcosines and derivatives thereof such as disclosed in U.S. Pat.Nos. 3,156,652 and 3,156,653; sulfurized fatty acids and esters thereofsuch as disclosed in U.S. Pat. Nos. 2,913,415 and 2,982,734; and estersof dimerized fatty acids such as disclosed in U.S. Pat. No. 3,039,967.The above-cited patents are incorporated herein by reference for theirdisclosure as pertinent to anti-chatter and anti-squawk agents useful asa functional additive in the emulsions of the present invention.

[0128] The emulsions of this invention may contain at least oneinhibitor for corrosion of metals. These inhibitors may preventcorrosion of either ferrous or non-ferrous metals (e.g., copper, bronze,brass, titanium, aluminum and the like) or both. The inhibitor may beorganic or inorganic in nature. Usually it is sufficiently soluble inwater to provide a satisfactory inhibiting action though it may functionas a corrosion-inhibitor without dissolving in water, thus it need notbe water-soluble. Many suitable inorganic inhibitors are known to thoseskilled in the art. Included are those described in “Protective Coatingsfor Metals” by Burns and Bradley, Reinhold Publishing Corporation,Second Edition, Chapter 13, pages 596-605. This disclosure relative toinhibitors are hereby incorporated by reference. Specific examples ofuseful inorganic inhibitors include alkali metal nitrites, sodium di-and tripolyphosphate, potassium and dipotassium phosphate, alkali metalborate and mixtures of the same. Many suitable organic inhibitors areknown to those of skill in the art. Specific examples includehydrocarbyl amine and hydroxy-substituted hydrocarbyl amine neutralizedacid compound, such as neutralized phosphates and hydrocarbyl phosphateesters, neutralized fatty acids (e.g., those having about 8 to about 22carbon atoms), neutralized aromatic carboxylic acids (e.g.,4-tertiarybutyl benzoic acid), neutralized naphthenic acids andneutralized hydrocarbyl sulfonates. Mixed salt esters of alkylatedsuccinimides are also useful. Useful amines include the alkanol aminessuch as ethanol amine, diethanolamine. Mixtures of two or more of any ofthe afore-described corrosion-inhibitors may be used. Thecorrosion-inhibitor is usually present in concentrations in which theyare effective in inhibiting corrosion of metals with which the inventiveemulsions come in contact.

[0129] In one embodiment, the emulsions of the present invention(particularly those that are used in cutting or shaping of metal)contain at least one polyol with inverse solubility in water. Suchpolyols are those that become less soluble as the temperature of thewater increases. They may function as surface lubricity agents duringcutting or working operations since, as the liquid is heated as a resultof friction between a metal workpiece and worktool, the polyol ofinverse solubility “plates out” on the surface of the workpiece, thusimproving its lubricity characteristics.

[0130] The emulsions of the present invention may contain otheradditives such as bactericides; dyes, e.g., an acid green dye; watersofteners, e.g., ethylene diamine tetraacetate sodium salt or nitrilotriacetic acid; odor masking agents, e.g., citronella, oil of lemon, andthe like; and anti-foamants, such as the well-known siliconeanti-foamant agents.

[0131] The emulsions may also include an anti-freeze additive where itis desired to use the composition at a low temperature. Materials suchas ethylene glycol and analogous polyoxyalkylene polyols can be used asanti-freeze agents. Clearly, the amount used will depend on the degreeof anti-freeze protection desired and will be known to those of ordinaryskill in the art.

[0132] Illustrative hydraulic fluids are provided in Table IV. In TableIV all numerical values are in parts by weight. TABLE IV A B C Productof Example 1 0.4 — — Product of Example 3 — 0.4 — Product of Example 7 —— 0.4 Mineral Oil 4 4 4 Water 95 95 95 Overbased calcium sulfonate 0.250.25 0.25 Dodecyl alcohol 0.25 0.25 0.25 Extreme pressure agent 0.250.25 0.25 (sulfurized olefin) Rust inhibitor (salt 0.05 0.05 0.05derived from dodecyl carboxylic acid and triethanol amine) Biocide(Busan 1060, a 0.05 0.05 0.05 product of Buckman Laboratories, Inc.identified as hexahydro- 1,3,5-tris(2-hydroxyethyl- S-triazine)

[0133] Acidizing Fluids

[0134] The emulsions of the invention may be used as acidizing inenhanced oil recovery processes. These acidizing fluids may be in theform of water-in-oil emulsions and may be comprised of a continuous oilphase, a discontinuous aqueous phase, an emulsifying amount of theinventive reaction produce, and a non-oxidizing acid.

[0135] The non-oxidizing acids include inorganic acids such ashydrochloric acid, sulfuric acid, hydrofluoric acid, sulfamic acid, andthe like, as well as organic acids containing from 1 to about 3 carbonatoms such as formic acid, acetic acid, propionic acid, and the lie.Mixtures of two or more of the foregoing acids may be used.

[0136] The oil phase may be present at a level in the range from about20% to about 70% by weight, and in one embodiment from about 40% toabout 60% by weight based on the total weight of the emulsion. Theaqueous phase may be present at a level in the range of from about 30%to about 80% by weight, and in one embodiment from about 40% to about60% by weight based on the total weight of the emulsion. The inventivereaction product may be present at a level in the range of from about 4%to about 40% by weight, and in one embodiment from about 10% to about20% by weight based on the total weight of the oil phase. Thenon-oxidizing acid may be present at a level in the range of from about10% to about 90% by weight, and in one embodiment from about 30% toabout 80% by weight of the total weight of the aqueous phase.

[0137] The acidizing fluids optionally may contain one or moreoil-soluble surfactants. These surfactants include anionic, cationic andnonionic surfactants. Suitable anionic surfactants include fatty acidsoaps which are the salts of long chain fatty acids derived fromnaturally occurring fats and oils and salts of alkylbenzene sulfonicacids. A useful anionic surfactant is the morpholinium salt oftetracosanylbenzene sulfonic acid. The ammonium and alkali metal saltsare also suitable. Cationic surfactants include amine salts such aspolyoxyethylene amine as well as quaternary ammonium compounds. Usefulcationic surfactants include high molecular weight alkyl imides andamides of polybasic amines. Suitable nonionic surfactants includederivatives of glycerides, glucosides, polyoxyethylene andpolyoxypropylene. Typical nonionic surfactants include ethoxylatedlinear alcohols and ethoxylated alkylphenols. Mixtures of surfactantsmay also be used. The acidizing fluids may contain up to about 10% byweight, and in one embodiment from about 0.1% to about 2% by weight ofthe foregoing surfactants.

[0138] The acidizing fluids may be prepared simply by mixing the oil,the water, the inventive reaction product and the non-oxidizing acid,and any other ingredient which may be desirable, in a homogenizer or anyother efficient blending device. Heating the emulsion during or after itis prepared is not necessary. The order of mixing of the ingredients isnot critical, although it is convenient first to prepare an oilconcentrate containing from about 50% to about 95% of the oil-solubleingredients and from about 5% to about 50% of the oil and then toemulsify the concentrate with a water solution containing thenon-oxidizing acid in appropriate proportions.

[0139] Reference is herein made to U.S. Pat. Nos. 4,140,640 and4,233,165 which disclose the preparation and use of water-in-oilacidizing fluids. These patents are incorporated herein by reference.

[0140] Illustrative acidizing fluids are provided in Table V. In Table Vall numerical values are in parts by weight. TABLE V A B Product ofExample 1  2 — Product of Example 7 —  2 Mineral Oil 48 48 37% Aqueoushydrochloric 50 50 acid solution

[0141] While the invention has been explained in relation to itspreferred embodiments, it is to be understood that various modificationsthereof will become apparent to those skilled in the art upon readingthe specification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modification as fall withinthe scope of the appended claims.

1. A composition comprising a partially dehydrated product made by: (I)reacting (A) a hydrocarbyl substituted succinic acid or anhydride with(B) a polyol, a polyamine, a hydroxyamine, or a mixture of two or morethereof, to form a first intermediate product comprising: an ester,partial ester or a mixture thereof when (B) is a polyol; an amide,imide, salt, amide/salt, partial amide or mixture two or more thereofwhen (B) is a polyamine; or an ester, partial ester, amide, partialamide, amide/salt, imide, ester/salt, salt or a mixture of two or morethereof when (B) is a hydroxyamine, a mixture of a polyol and apolyamine, a mixture of polyol and a hydroxyamine, a mixture of apolyamine and a hydroxyamine, or a mixture of a polyol, a polyamine anda hydroxyamine; the hydrocarbyl sustitutent of said acid or anhydridehaving an average of about 8 to about 200 carbon atoms; and (II) heatingsaid first intermediate product at an effective temperature to form asecond intermediate product with water of reaction being formed, andseparating a portion of said water of reaction from said secondintermediate product to form said partially dehydrated product, when (A)is said succinic anhydride the amount of water of reaction that isseparated is from about 0.2 to about 0.9 moles of said water of reactionper equivalent of said succinic anhydride, when (A) is said succinicacid the amount of water of reaction that is separated is from about 1.2to about 1.9 moles of said water of reacting per equivalent of saidsuccinic acid, said partially dehydrated product having a total acidnumber in the range of about 20 to about 100 mg of KOH/g.
 2. Thecomposition of claim 1 wherein said hydrocarbyl substituent has anaverage of about 18 to about 30 carbon atoms.
 3. The composition ofclaim 1 wherein a mixture of at least two hydrocarbyl substitutedsuccinic acids or anhydrides is used, the hydrocarbyl substituent of oneof said acids or anhydrides having an average of about 12 to about 24carbon atoms, and the hydrocarbyl substituent of another of said acidsor anhydrides having an average of about 60 to about 200 carbon atoms.4. The composition of claim 1 wherein said hydrocarbyl substitutedsuccinic acid or anhydride consists of hydrocarbyl substituent groupsand succinic groups and is characterized by the presence within itsstructure of at least about 1.3 succinic groups for each equivalentweight of the hydrocarbyl substituent.
 5. The composition of claim 1wherein said polyol is a compound represented by the formulaR—(OH)_(m)  (I) wherein in Formula (I), R is an organic group having avalency of m, R is joined to the OH groups through carbon-to-oxygenbonds, and m is an integer from 2 to about
 10. 6. The composition ofclaim 1 wherein said polyol is a glycol, a polyoxyalkylene glycol, acarbohydrate, or a partially esterfied polyhydric alcohol.
 7. Thecomposition of claim 1 wherein said polyol is ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, propyleneglycol, dipropylene glycol, tripropylene glycol, dibutylene glycol,tributylene glycol, 1,2-butanediol, 2,3-dimethyl-2,3-butanediol,2,3-hexanediol, 1,2-cyclohexanediol, pentaerythritol, dipentaerythritol,1,7-heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol,1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol,1,2,4-butanetriol, 2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol,1,10-decanediol, digitalose,2-hydroxymethyl-2-methyl-1,3-propanediol-(trimethylolethane), or2-hydroxymethyl-2-ethyl-1,3-propanediol-(trimethylopropane).
 8. Thecomposition of claim 1 wherein said polyol is a sugar, a starch, or amixture thereof.
 9. The composition of claim 1 wherein said polyol iserythritol, threitol, adonitol, arabitol, xylitol, sorbitol, mannitol,erythrose, fucose, ribose, xylulose, arabinose, xylose, glycose,fructose, sorbose, mannose, sorbitan, glucosamine, sucrose, rhamnose,glyceraldehyde or galactose.
 10. The composition of claim 1 wherein saidpolyol is a compound represented by the formula HO(CH₂CH(OH)CH₂O)_(n)Hwherein n is a number in the range of 1 to about
 5. 11. The compositionof claim 1 wherein said polyol is a polyhydric alcohol having at leastthree hydroxyl groups, some of the hydroxyl groups being esterfied withan aliphatic monocarboxylic acid of about 8 to about 30 carbon atoms, atleast two of the hydroxyl groups not being esterfied.
 12. Thecomposition of claim 1 wherein said polyol is monooleate of glycerol,monostearate of glycerol, monooleate of sorbitol, distearate ofsorbitol, or di-dodecanoate of erythritol.
 13. The composition of claim1 wherein said polyamine is an aliphatic, cycloaliphatic, heterocyclicor aromatic compound.
 14. The composition of claim 1 wherein saidpolyamine is a compound represented by the formula

wherein n has an average value between 1 and about 10, the Alkylenegroup has from 1 to about 10 carbon atoms, and each R is independentlyhydrogen or an aliphatic or hydroxy-substituted aliphatic group of up toabout 30 carbon atoms.
 15. The composition of claim 1 wherein saidpolyamine is ethylene diamine, triethylene tetramine,tris-(2-aminoethyl)amine, propylene diamine, trimethylene diamine,tripropylene tetramine, tetraethylene pentamine, hexaethylene heptamine,pentaethylenehexamine, or a mixture of two or more thereof.
 16. Thecomposition of claim 1 wherein said polyamine is an ethylene polyamine.17. The composition of claim 1 wherein said polyamine is a heterocyclicamine.
 18. The composition of claim 1 wherein said hydroxyamine is (a)an N-(hydroxyl-substituted hydrocarbyl) amine, (b) ahydroxyl-substituted poly(hydrocarbyloxy) analog of (a), or a mixture of(a) and (b).
 19. The composition of claim 1 wherein said hydroxyamine isan alkanolamine containing from 1 to about 40 carbon atoms.
 20. Thecomposition of claim 1 wherein said hydroxyamine is selected from thegroup consisting of (a) primary, secondary or tertiary alkanol aminesrepresented respectively by the formulae

(b) hydroxyl-substituted poly(hydrocarbyloxy) analogs of said primary,secondary or tertiary alkanolamines represented respectively by theformulae

wherein each R independently is a hydrocarbyl group of one to about 8carbon atoms or a hydroxyl-substituted hydrocarbyl group of 2 to about 8carbon atoms, each R′ independently is a divalent hydrocarbon group of 2to about 18 carbon atoms, and each x independently is 2 to about 15, and(c) mixtures of two of more of any of the above.
 21. The composition ofclaim 1 wherein (B) is glycerol, diethanolamine, triethanol amine, or amixture of two or more thereof.
 22. The composition of claim 1 whereinthe ratio of equivalents of component (A) to component (B) is about 3:1to about 1:2.
 23. A composition comprising a partially dehydratedproduct made by: (I) reacting (A) a hydrocarbyl substituted succinicacid or anhydride with (B) a polyamine, a hydroxyamine, a mixture of apolyol and a polyamine, a mixture of a polyol and a hydroxyamine, amixture of a polyamine and a hydroxyamine, or a mixture of a polyol, apolyamine and a hydroxyamine, to form a first intermediate productcomprising: an amide, imide, salt, amide/salt, partial amide or mixturetwo or more thereof when (B) is a polyamine; or an ester, partial ester,amide, partial amide, amide/salt, amide, ester/salt, salt or a mixtureof two or more thereof when (B) is a hydroxyamine, a mixture of a polyoland a polyamine, a mixture of a polyol and a hydroxyamine, a mixture ofa polyamine and a hydroxyamine, or a mixture of a polyol, a polyamineand a hydroxyamine; the hydrocarbyl sustitutent of said acid oranhydride having an average of about 8 to about 200 carbon atoms; and(II) heating said first intermediate product at an effective temperatureto form a second intermediate product with water of reaction beingformed, and separating a portion of said water of reaction from saidsecond intermediate product to form said partially dehydrated product,when (A) is said succinic anhydride the amount of water of reaction thatis separated is from about 0.2 to about 0.9 moles of said water ofreaction per equivalent of said succinic anhydride, when (A) is saidsuccinic acid the amount of water of reaction that is separated is fromabout 1.2 to about 1.9 moles of said water of reaction per equivalent ofsaid succinic acid, said partially dehydrated product having a totalacid number in the range of about 20 to about 100 mg of KOH/g.
 24. Aprocess, comprising: (I) reacting (A) a hydrocarbyl substituted succinicacid or anhydride with (B) a polyol, a polyamine, a hydroxyamine, or amixture of two or more thereof, to form a first intermediate productcomprising: an ester, partial ester or mixture thereof when (B) is apolyol; an amide, imide, salt, amide/salt, partial amide or mixture oftwo or more thereof when (B) is a polyamine; or an ester, partial ester,amide, partial amide, amide/salt, imide, ester/salt, salt or a mixtureof two or more thereof when (B) is a hydroxyamine, a mixture of a polyoland a polyamine, a mixture of a polyol and a hydroxyamine, a mixture ofa polyamine and a hydroxyamine, or a mixture of a polyol, a polyamineand a hydroxyamine; the hydrocarbyl substituent of said acid oranhydride having an average of about 8 to about 200 carbon atoms; and(II) heating said first intermediate product at an effective temperatureto form a second intermediate product with water of reaction beingformed, and separating a portion of said water of reaction from saidsecond intermediate product, when (A) is said succinic anhydride theamount of water of reaction that is separated is from about 0.2 to about0.9 moles of said water of reaction per equivalent of said succinicanhydride, when (A) is said succinic acid the amount of water ofreaction that is separated is from about 1.2 to about 1.9 moles of-saidwater of reaction per equivalent of said succinic acid, said partiallydehydrated product having a total acid number in the range of about 20to about 100 mg of KOH/g.
 25. A concentrate comprising about 10% toabout 90% by weight of a normally liquid organic diluent, and thecomposition of claim
 1. 26. An emulsion, comprising: an organic phase;an aqueous phase; and an emulsifying amount of the composition ofclaim
 1. 27. An emulsion, comprising: a continuous organic phase, adiscontinuous aqueous phase, and an emulsifying amount of thecomposition of claim
 1. 28. A high internal phase emulsion, comprising:a continuous organic phase, a discontinuous aqueous phase, and anemulsifying amount of the composition of claim 1, the weight ratio ofsaid aqueous phase to said organic phase being at least about 4:1. 29.An explosive emulsion, comprising: a discontinuous oxidizer phasecomprising water and an oxygen-supplying component; a continuous organicphase comprising a carbonaceous fuel; and an emulsifying amount of thecomposition of claim
 1. 30. An emulsion fertilizer, comprising: adiscontinuous aqueous fertilizer phase comprising at least one watersoluble fertilizer component; a continuous organic phase comprising atleast one oil; and an emulsifying amount of the composition of claim 1.31. A water-blended fuel composition, comprising: a discontinuousaqueous phase; a continuous fuel phase comprising a normally liquidhydrocarbon fuel; and an emulsifying amount of the composition ofclaim
 1. 32. A lubricant or functional fluid, comprising: an oil phase,an aqueous phase, an emulsifying amount of the composition of claim 1,and at least one functional additive.
 33. An acidizing fluid,comprising: a continuous oil phase, a discontinuous aqueous phase, anemulsifying amount of the composition of claim 1, and a non-oxidizingacid.